Lubricants for cold rolling and manufacturing the same

ABSTRACT

A LUBRICANT FOR COLD ROLL IS DISCLOSED WHICH COMPRISES AN ADDITION PRODUCT OF AN EPOXY COMPOUND AND AN OXIDATION PRODUCT OF AN ALIPHATIC HYDROCARBON HAVING AN ACID VALUE OF 30 TO 110; SAID ADDITION PRODUCT HAVING AN ACID VALUE OF 0 TO 30 AND CONTAINING SAID EPOXY COMPOUND IN THE MOLECULE IN AN AMOUNT SUFFICIENT TO REDUCE AT LEAST 60 PERCENT OF THE ACID VALUE OF SAID OXIDATION PRODUCT; AND SAID OXIDATION PRODUCT OF THE HYDROCARBON BEING PREPARED BY CONTACTING AT 100 TO 180*C. AN ALIPHATIC HYDROCARBON HAVING 15 TO 55 CARBON ATOMS WITH MOLECULAR OXYGEN.

United States Patent Oflice 3,654,156 Patented Apr. 4, 1972 US. (:1.252-495 6 Claims ABSTRACT or THE DISCLOSURE A lubricant for cold roll isdisclosed which comprises anraddition product of an epoxy compound andan oxidation'product of an aliphatic hydrocarbon having an acid value of30to 110; said additionproduct having an acid value of to 30 andcontaining said epoxy compound in the molecule in an amount sufficientto reduce at least 60 percent of the acid value of said oxidationproduct; and said oxidation product of the hydrocarbon being prepared bycontacting at ,100 to 180 C. an aliphatic hydrocarbon having 15 to 55carbon atoms with molecular oxygen.

This invention relates to a lubricant for cold rolling and a process formanufacturing the same.

" In the cold rolling of steel strip, it is necessary to apply alubricant on the strip which passes through the pressure rolls. Thequality of the lubricant used determines, to a large extent, the speedat which the mills are to be operated and the pressure to be applied asWell as the flatness, surface appearance and characteristics of theresultant cold rolled sheet.

Therefore, it is desired for'the lubricant to have the followingproperties:'

1) Causinglittle or no oil stains during a cold rolling step,therebymaking it possible to produce a metal sheet having good surfaceappearance;

(2) Having a low order of mean yield stress, so as to reduce the rollpressure required for the production of a rolled metal sheet having adesired thickness; and

(3) Having low viscosity and good water-dispersibility, so that thelubricant can be spread quickly and completely under operatingconditions in which Water is used as a coolant in connection therewith.

In the prior art palm oil has been widely used as a lubricant for coldrolling, but it fails to meet the requirements of todays cold rollingprocedures which call for higher speed because of the progress inrolling techniques.

' For instance, the mean yield stress of palm oil is not sufiicientlylow and the Water-dispersibility thereof is somewhat poorfor use-in thehigh-speed rolling of today. Further, it causes, considerable undesiredoil stains during the high-speed cold rolling step.

To eliminate the drawbacks of palm oil as above mentioned many attemptshave beenmade, but none of the lubricants so far proposed have proved tobe superior to palm oil.

It is an object of the invention, accordingly, to provide a lubricanthaving improved properties for cold rolling as compared to palm oil.

Another object'of the invention is to provide a lubricant which willmeet the severe rolling'mills.'--

requirements of high-speed v A further object of the invention is toprovide a method for producing a lubricant having the abovecharacteristics from materials available in large quantities.

These and other objects of the invention will be apparent from thedescription to follow.

According to the present invention, specific addition products of epoxycompounds and oxidation products of aliphatic hydrocarbons having anacid value of 30 to are used as lubricant for cold rolling.

The specific addition products of the invention are prepared by theaddition reaction of epoxy compounds and oxidation products of aliphatichydrocarbons having an acid value of 30 to 110. The addition productshould have an acid value of 0 to 30 and contain the epoxy compounds inthe molecules in an amount sufficient to reduce at least 60 percent ofthe acid value of the oxidation products. This reduction rate of theacid value is determined by the following equation:

Reduction rate of acid value (percent)= 2 X 100 in which A is the acidvaluve of the oxidation product and B is the acid value of the resultantaddition product.

The present inventors have found that when the above specific additionproduct is used as a lubricant for cold rolling it displays excellentlubricating effects, superior to those of palm oil.

For example, the mean yield stress thereof is lower than that of palmoil. Further, it causes less oil stains even in high-speed rolling andcan be spread quickly and completely even under operating conditions inwhich water is used as a coolant.

The oxidation products of hydrocarbons used for the production of theabove specified addition products are prepared by contacting at 100 to180 C. aliphatic hydrocarbons having 15 to 55 carbon atoms withmolecular oxygen.

The starting saturated aliphatic hydrocarbons of having 15 to 55 carbonatoms are available in large quantities and representatives thereof are,for example, parafiin wax, low polymers of ethylene, paraffins obtainedby the thermal decomposition of long chain n-paraffins, etc. Accord ingto the present invention the aliphatic hydrocarbons are oxidized bycontacting them with molecular oxygen to produce oxidation products ofhydrocarbons having an acid value of 30 to 110. For the molecularoxygen, oxygen gas may be used alone or in combination with a diluentgas, such as nitrogen, argon, carbon dioxide, steam, etc. When theoxygen gas is diluted it is preferable that the resultantoxygen-containing gas contains oxygen in at least 5 percent by volume.Air is the most desirable source of the molecular oxygen. The oxidationreaction of the hydrocarbons with the molecular oxygen is a gas-liquidphase reaction in which oxygen-containing gas is brought into contactwith liquid hydrocarbons melted if necessary. In the present processvarious conventional methods may be employed for contacting the gas withthe liquid. For instance, oxygen-containing gas, such as air, may becontacted with hydrocarbons by blowing it into liquid hydrocarbonsthrough porous materials or it may be contacted therewith by shaking theliquid in the oxygen-containing gas atmosphere or by using an ejector,turbine. or a like. conventional device for contacting gas with liquid.

The reaction temperature of the oxidation reaction should be in therange of 100 to 180 C. At lower temperatures the reaction cannot proceedeffectively,

while at higher temperatures undesired decomposition of the startinghydrocarbons occursYThe preferred reaction temperature is in the rangeof to C. The. reaction pressure is usually atmospheric pressure, thoughincreased or reduced pressures may also be employed. To accelerate thereaction various catalysts may be used, as required. Examples thereofare peroxides, azo compounds, or salts or oxides of transition metals,such as manganese, chromium, vanadium, cobalt, nickel, copper, lead,iron etc. The reaction time may vary in accordance with the reactionconditions, but usually 0.5 to 50 hours reaction is sufficient to effectthe desired result.

By gas chromatographic and infrared spectroscopic analyses and themeasurement of molecular weight, acid value, saponification value,hydroxyl value, carbonyl value and iodine value the resultant oxidationproducts have been determined to be a mixture of various compoundshaving different molecular weight and structures. The molecules comprisesuch functional groups as carboxyls, carbonyls and hydroxyls dependingupon the degree of oxidation thereof. Therefore, the structural formulaof the oxidation products of the hydrocarbons cannot be preciselydefined. The present inventors, however, have found that the acid valueof the resultant oxidation products is an important factor in producingthe specific addition products useful for the present invention and thatwhen the acid value is in the range of 30 to 110 a desirable lubricationcan be obtained by the subsequent addition reaction referred tohereinbefore and hereinafter. The lubricant of the present inventioncannot be produced from oxidation products having lower or higher acidvalues. For example, oxidation products having an acid value of lowerthan 30 result in the production of a lubricant having high degree ofmean yield stress as well as high friction resistance, which areundesirable, while oxidation products of acid values of higher than 110result in the production of undesired resinous byproducts. The preferredacid value of the oxidation product is in the range of 50 to 100. Theoxidation products of the present invention having a 30 to 110 acidvalue usually have a saponification value of 60 to 400 and an averagemolecular weight of 250 to 800. The characteristics, however, are not socritical in the production of the present lubricant and may vary over awide range ac cording to the starting hydrocarbons and the oxidationconditions applied.

The resultant oxidation product of the aliphatic hydrocarbon issubsequently reacted with epoxy compounds as it is or after removing lowboiling byproducts, whereby the epoxy group in the epoxy compound isreacted with the carboxyl group in the oxidation products to produce thedesired addition compound.

The epoxy compounds used in the invention are represented by thefollowing formula:

wherein R is one member of the group consisting of hydrogen atom, alkylgroup of 1 to carbon atoms, hydroxymethyl group, chloromethyl group,acyloxymethyl group of 2 to 7 carbon atoms, carboalkoxylrnethyl group of2 to 7 carbon atoms, alkoxymethyl group of 2 to 7 carbon atoms,phenoxymethyl group and phenyl group; and R and R are respectively onemember of the group consisting of hydrogen atom and a lower alkyl groupof l to 3 carbon atoms; and when R and R are alkyl and R is hydrogen Rand R may constitute a cycloalkyl group by being bonded to each other attheir end positions. Representative compounds are, for example,epoxyethane, epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane,epoxyisobutane, 1,2-epoxyhexane, 1,2-epoxydodecane, 4,5- epoxydodecane,1-oxy-2,3-epoxypropane, epichlorohydrin, 1,2epoxycyclohexane, styreneoxide, phenyl glycidyl ether and the like.

Of these epoxy compounds the most desirable compounds are those havingthe structural formula in which R is hydrogen or a lower alkyl group of1 to 2 carbon atoms and R and R are hydrogen. Representative compoundsare epoxypropane and 1,2-epoxybutane.

The addition reaction may be carried out in the presence or absence ofcatalysts at a temperature higher than the melting point of theoxidation products of the hydrocarbons. The epoxy compound may be usedin an amount necessary for reducing at least 60 percent of the acidvalue of the oxidation product and for producing addition products withan acid value of O to 30. Such an amount may be determined from the acidvalue of the oxidation product, since it has been determined that theacid value of the oxidation products is in proportion to the number ofthe carboxyl groups contained in the oxidation product and the epoxycompound is reacted with the carboxyl groups to reduce the acid value.Though from a theoretical viewpoint one mole of the epoxy com pound willreact with one of the carboxyl groups, part of the epoxy compound usedmay be self-polymerized, so that the epoxy compound preferably is usedin an excess amount. Usually it is used in the calculated amount or inan excess amount not higher than 200 percent of the calculated amount(mole). Most preferably the epoxy compound is used in 10 to 30 percentexcess in the calculated amount. The reaction temperature may usually bebetween 60 and 250 C., and is preferably between and C. The reactionpressure may vary over a wide range, but usually it may be atmosphericpressure or an increased pressure of less than 20 kg./cm. To acceleratethe reaction conventional catalysts used in the polymerization of epoxycompounds may be-used. Examples of the catalysts are triethyl amine,tributyl amine, pyridine, tributyl phosphate, potassium phosphate,ammonium phosphate, triethyl phosphite, phosphoric acid, sulfuric acid,boron trifiuoride, sodium hydroxide, potassium hydroxide, calciumhydroxide, calcium oxide, manganese oxide, etc. The reaction may becarried out in the presence or absence of inert solvents, such asbenzene, toluene, xylene petroleum ether and the like.

The reaction time may vary in accordance with the reaction conditionsapplied, but usually 0.5 to 30'hour's reaction is sufiicient for thepurpose.

By gas chromatographic and infrared spectroscopic analyses and themeasurement of molecular weight, acid value, saponification value,carbonyl value and hydroxyl value, the resultant addition product hasbeen found to be a mixture of various products. The epoxy compound isadded to the oxidation products of hydrocarbons resulting in differentstructures depending on the degree of the oxidation, so that as with theoxidation products, it is impossible to determine the precise structureof the addition product. The present inventors, however, have found thatthe resultant addition product is useful as a lubricant for cold rollingand meets the severe require: ments of the recent high-speed rollingmills, when the acid value thereof is within the range of 0 to 30 andthe reduction rate of the acid value defined before is more than 60percent, irrespective of other characteristics of the additioncompounds. The preferable acid value of the addition compound is from 2to 20. Though the addition products may contain byproducts such aspolymers of the epoxy compound, there is no need to remove them as theamount thereof is small and such byproducts do not adversely affect thelubricating properties of theaddition compounds.

In fact, when the present addition product having an acid value of 0 to30 is used as lubricant for cold rolling it displays markedadvantagesover those. of palm oil and can advantageously be used as alubricant for cold rolling at high speeds without any objections. Theaddition product of the invention desirably has an average molecularweight of 280 to 800.

The addition product may be used as a lubricant for cold rolling as itis, but it is usually to be used in the form of an aqueous dispersionand the addition compound is usually in a concentration of 1 to 30 wt.percent, preferably to 25 wt. percent. The lubricant of the inventioncan-be used" for the cold rolling of steel sheets and plates havingvarious thicknesses.

For. example, it displays excellent lubricating effects even in coldrolling for producing steel sheet less than 0.19 mm. in thickness. Itmay also be admixed with animal or vegetable oil-based lubricants, suchas tallow, lard, whale oil, palm oil, castor oil or rape seed oil, in anamount of 1 to 30'percent' by weight to improve the lubricatingproperties thereof. In fact, such admixed oils can effectively be usedin cold rolling for producing steel sheets of 0.19 to 0.30 mm. inthickness and gives better results as compared with use of the animal orvegetable oil-based lubricants alone. For the production of thickersteel plates, the lubricant of the invention may be admixedin an amountof 1 to 30 percent by weight with a conventional petroleum lubricant toimprove the lubricating properties thereof.

To the lubricant of the invention there may be added conventionaladditives, such as rust inhibitors, surfactants, extreme pressureadditives, antioxidants, antifoaming agents, etc.

For better understanding of the invention examples are given below.

EXAMPLE 1 Petroleum parafiin Wax having an average of 27 carbon atomsper molecule was melted at 60 C., and manganese naphthenate was added ina proportion of mole per kilogram of the wax. kg. of the mixture thusobtained was placed in a cylindrical stainless steel reactor of 250 mm.in diameter, and 3,000 mm. in height and, while heating the mixture at160 C., air was blown from the bottom of the reactor in a proportion of2 l./min./kg. of the wax for hours. 14.25 kg; of product was obtained.

By gas chromatographic and infrared spectroscopic analyses the substancethus obtained was determined to be a mixture of various oxidationproducts having different structuresand it 'had the followingcharacteristics: Melting pointi'41? C."

Acid'value': 68.0 Saponification value: 243.5

To 12.5 kg. of the resultant oxidation product melted at 60 C. was added56.4 g. of a 50 weight percent aqueous solution of potassium hydroxideand the mixture was placed in -a 20 liter autoclave. To the mixture wasadded 800 grams of epoxyethane and the resultant mixture was heated withstirring at 135 C. under a pressure of 4 kg./cm. for 5 hours. Removal ofthe unreacted epoxyethane gave 13.2 kg. of waxysubstance.

By gas chromatographic andinfrared spectroscopic analyses the resultantsubstance was determined to be a mixture of various addition products ofthe oxidation product and epoxyethane, and it had the followingcharacteristics:

Melting point: -39 C.

Acid value: 20.0

Saponification 'value: 220

Melt viscosity (at 50C.): 89 cst.

EXAMPLE 2 12.5 kg. of an oxidation product prepared in the same manneras in Example 1 was reacted with 1 kg. of epoxyethane in the same manneras in. Example 1, whereby 13.1 kg. of addition product having thefollowing characteristics was obtained.

Melting point: 38 C.

Acid value: 10.8

Saponification value 206' Melt'viscosity'(at 50 C.): 84 cst.

EXAMPLE 3 12.5 kg. of an oxidation product prepared in the same manneras in Example 1 was reacted with 1.13 kg. of

epoxyethane in the same manner as in Example 1, whereby 13.2 kg. ofaddition product having the following characteristics was obtained.

Melting point: 36 C.

Acid value: 2.5

Saponification value: 202

Melt viscosity (at 50 C.): 79 cst.

In 80 parts by weight of water were dispersed 20 parts by Weight of therespective addition products of Examples 1 to 3 to produce lubricantsfor cold rolling.

For comparison four kinds of lubricants were prepared in the same manneras above by dispersing the followin substances in water respectively.

Comparison 1: Palm oil Comparison 2: Oxidation product of hydrocarbonprepared in the same manner as in Example 1.

Comparison 3: Addition product of the oxidation product of hydrocarbonas in Example 1 with epoxy ethane, which was prepared in the same manneras in Example 1 except that 66.5 g. of epoxy ethane was used.

Comparison 4: Addition product of the oxidation product of hydrocarbonas in Example 1 with epoxy ethane, which was prepared in the same manneras in Example 1 except that 335 g. of epoxy ethane was used.

The respective lubricants thus prepared were used as lubricants for coldrolling and the rate of oil stain, mean yield stress andwater-dispersibility thereof were measured by the following methods,with the results shown in Table 1 below:

(Rate of oil stain) Each lubricant was uniformly sprayed on a steelplate, 10 x 10 cm., at the rate of 0.5 g./cm. Thereafter another steelplate of the same size was placed on it and left under pressure of 13ton/ cm. at C. for 12 hours. The area (percent) of oil stain created wasmeasured and the rate of oil stain was determined by the followingequation:

Rate of oil stain (percent) Area of oil stain created (cm?) (Mean yieldstress) Mild steel sheet of 30 mm. in width and 1 mm. in thickness wasrolled by pressure rolls of mm. in diameter and 200 mm. in Width at arolling speed of 13 m./min. and at a temperature of 60 to 65 C. forthree turns. The curve of reduction-mean yield stress was obtained inknown manner and the mean yield stress at 75' percent reduction is shownin Table 1 below.

(Water-dispersibility) The respective lubricants, immediately afterpreparation were left to stand at room temperature for 5 minutes, andthe volume of the layer separated was measured.

No'rn.E.O. (moles) represents number of mole of ethylene oxide used perone COOH group in oxidation product.

7 EXAMPLE 4 15 g. of potassium permanganate was added to 10 kg.petrolatum having a melting point of 54 C. and heated to a temperatureof 120 C. The mixture was placed in a 20 liter autoclave. Then themixture was heated at 150 C., into which air was blown in a proportionof 2 l./min./kg. of the petrolatum for 20 hrs. The pressure in theautoclave was maintained at 2.5 kg./cm. 9.8 kg. of product was obtained.

By gas chromatographic and infrared spectroscopic analyses the substancethus obtained was determined to be a mixture of various oxidationproducts and it had the following characteristics:

Melting point: 50 C.

Acid value: 89

Saponification value: 258

Melt viscosity (at 100 C.): 167 cst.

Melting point: 47 C.

Acid value: 11

Saponification value: 254.1

Melt viscosity (at 100 C.): 162 cst.

parts by weight of the resultant addition product was dispersed in 95parts by weight of water, and the rate of oil stain and mean yieldstress of the lubricant thus obtained were measured in the same mannerdescribed with reference to Examples 1 to 3, with the following results.

Rate of oil stain (percent): 5 Mean yield stress (kg/mini): 130

EXAMPLE 5 1 kg. of paraffin having a melting point of 38 C. and anaverage of 18 carbons per molecule was melted at 60 C., to which g. ofbenzoic peroxide was added, and the mixture was placed in a 2 literflask. The resultant mixture was heated at 110 C. and air was blown intothe mixture in proportion of 2 l./min./kg. of the paraffin for 3 hours.1.01 kg. of oxidation product having the following characteristics wasobtained.

Melting point: 33 C.

Acid value: 49

Saponification value: 161

Melt viscosity (at 100 C.): 25.4 cst.

1 kg. of the resultant oxidation product was melted at 80 C., to whichwas added 20* g. of a weight percent ether solution of trifluoroboronethylate, and the mixture was placed in a 2 liter autoclave. To themixture 220 g. of epoxypropane was added and the resultant mixture washeated with stirring at 120 C. under pressure of 4.5 kg./cm. for 2hours. 1.1 kg. of addition product having the following characteristicswas obtained.

Melting point: 31 C.

Acid value: 4.5

Saponification value: 154

Melt viscosity (at 100 C.): 18.6 cst.

10 parts by weight of the resultant addition product was dispersed in 90parts by weight of water, and the mean yield stress of the resultantlubricant measured in the same manner as described with reference toExamples 1 to 3 was 149 kg./mm.

' Melt viscosity (at C 24.5 cst.-

8 EXAMPLE 6 Melting point: 41 C.

Acid value: 72 Saponification value: 241 Melt viscosity (at 100 C.):38.3 cst.

The resultant oxidation product wasmeltedat 60. C., 5.0 g. of sodiumethoxide was added, and the mixture was placed in a 2 liter flask. Tothe mixture 113 g. of epoxyethane was added and the resultantrnixturewas heated with stirring at 160 C. for 4 hours, whereby 830 kg. of anaddition product having thetfollowing characteristics was obtained.

Melting point: 40 C.

Acid value: 21

Saponification value: 198

Melt viscosity (at 100 C.): 34.1 cst.

In 80 parts by weight of water was dispersed 20 parts" by weight of theresultant additionproduct, and the rate of oil stain and meany'ieldstress of the lubricant thus obtained were measured'in the same manneras described with reference to Examples 1 to 3, with the followingresults.

Rate of oil stain 5 Mean yield stress (kg/mmP): 137 7 EXAMPLE 7 10 kg.of normal paraffin havinga melting pointof 49 C. and an average of 22carbons per moleculewas melted at 60 C., to which was added 122.5 ml. ofa 5 weight percent kerosene solution of manganese naphthenate. Themixture was placed in a cylindrical reactor of 250 mm. in diameter and3,000. mmu-in'height. The mixture was heated at 170 C. and air was blownfrom the bottom of" the reactor in a proportion of 20 l./min./kg. of theparafiin for 6 hours. 70kg. of oxidation product having the followingcharacteristics was obtained. Melting point: 31 C. i Acid value:

Saponification value: 320 p Melt viscosity (at 100 C.): 27.1 cst.

1 kg. of the resultant oxidation product was placed in a 2 literstainless steel autoclave and melted at 60 C., and

3 g. of potassium hydroxide was added. To the mixture 257 g. ofepoxyisobutane was added and the resultant mixture was heated withstirring at C. under pres-. sure of 6 kg./cm. for 10 hours, whereby 1.2kg. of addi-U tion product having the following characteristics wasobtained:

Melting point: 29 C. 7 Acid value: 5.0 I, Saponification value: .302

In 80 parts by weight of water was dispersed 20 parts by weight of theresultant addition product, and the-rateof oil stain and mean yieldstress of the lubricant thus obtained were measured in the same manneras described with reference to Examples 1 to 3, with theresultsshownbelow.

Rate of oil stain 3 Mean yield stress (kg/mun): 133

9 EXAMPLE 3 1 kg. of an oxidation product prepared in the same- In 80parts by weight of water was dispersed 20 parts by weight of theresultant addition product, and the mean yield stress ofthe lubricantmeasured in the same manner as described with reference to Examples 1 to3 was 134 kg./mm.-.

. EXAMPLE 9 1.5 kg. of an oxidation product prepared in the same manneras in Example 7 was melted at 60 C., and 6 g. of triethylamine was addedthereto. The mixture was placed in a 3 liter stainless steel autoclave.To the mixture 250.5 g. of 1-oxy-2,3-epoxypropane wasadded and theresultant mixture was heated with'stirring at 90 C. under pressure ofkg/cm. for 0.5 hour. 1.65 kg. of addition product having the'followingcharacteristics was obtained.

Melting point: 30 C.

Acid value: 5.0

Saponification value: 311

Melt viscosity (at 100C): 26.1 cst.

In 80 parts byweight of water was dispersed 20 parts by weight of theresultant addition product, and the rate of oil stain and mean yieldstress of the lubricant thus obtained were measured in the same manneras described with reference to Examples '1 to 3, with the results shownbelow: .1

Melting point: 30 C.

Acid value: 3

Saponification value: 306

Melt viscosity (at 100 C.): 25.5 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of theresultant addition product, and the rate of oil stain and mean yieldstress of the lubricant thus obtained were measured in the same manneras described with reference to Examples 1 to 3, with the followingresult.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm. 133

EXAMPLE 1 1 kg. of normal paraflin having a melting point of 49 C. andan average of 22 carbons per molecule was melted at 60 C., to which wasadded 122.5 ml. of a 5 weight percent kerosene solution of manganesenaphthenate, and the mixture was placed in a cylindrical stainless steelreactor of 250 mm. in diameter and 3,000 mm. in height. The mixture washeated at 170 C. and air was blown from the bottom of the reactor in aproportion of 30 10 l./min./kg. of the paraffin. 8.4 kg. of oxidationproduct having the following chracteristics was obtained.

Melting point: 40 C.

Acid value: 40

Saponification value: 148

Melt viscosity (at C.): 8.8 cst.

1 kg. of the resultant oxidation product was melted at 60 C., to which10 g. of phosphoric acid was added, and the mixture was placed in a 2liter autoclave. To the mixture 167 g. of styrene oxide was added andthe resultant mixture was heated with stirring at 160 C. under pressureof 4 kg./cm. for 5 hours. 1.1 kg. of addition product having thefollowing characteristics was obtained.

Melting point: 39 C.

Acid value: 22

Saponification value: 138

Melt viscosity (at 100 C.): 7.2 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of theresultant addition product, and the rate of oil stain and mean yieldstress of the lubricant thus obtained were measured in the same manneras described with reference to Examples 1 to 3, with the followingresults.

Rate of oil stain (percent): 3 Mean yield stress (kg./mm.

EXAMPLE 12 1 kg. of an oxidation product prepared in the same manner asin Example 11 was melted at 60 C., to which 5 g. of trietthylphosphitewas added, and the mixture was placed in a 2 liter autoclave. To themixture 119 g. of phenylglycidyl ether was added and the resultantmixture was heated with stirring at 120 C. under pressure of 4 kg./cm.for 8 hours, whereby 1.1 kg. of an addition product having the followingcharacteristics was obtained.

Melting point: 38 C.

Acid value: 18

Saponification value: 129

Melt viscosity (at 100 C.): 8.6 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of theaddition product, and the rate of oil stain and mean yield stress weremeasured in the same manner as described with reference to Examples 1 to3, with the following results.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm.

EXAMPLE 13 1 kg. of an oxidation product prepared in the same manner asin Example 11 was melted at 60 C., to which 3 g. of potassium hydroxidewas added, and the mixture was placed in a 2 liter autoclave. To themixture 120 g. of 1,2-epoxycyclohexane was added and the resultantmixture was heated with stirring at C. under pressure of 4 kg./cm. for10 hours. 1.1 kg. of addition product having the followingcharacteristics was obtained.

Melting point: 38 C.

Acid value: 12

Saponification value: 117

Melt viscosity (at 100 C.): 8.1 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of theresultant addition product, and the rate of oil stain and mean yieldstress of the lubricant thus obtained were measured in the same manneras described with reference to Examples 1 to 3, with the following resuts.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm. 148

What we claim is: 1. process for cold rolling a metal which comprisesapplying between the roll and the metal a lubricating 1 1 amount of theadditionproduct of an epoxy compound and an oxidation product of analiphatic hydrocarbon having an acid value of 30 to 110; said additionproduct having an average molecular weight of 280 to 800 and an acidvalue of to 30 and containing said epoxy compound in the molecule in anamount from 1 to 2 moles per mole of carboxyl group inthe oxidationproduct but sufficient to reduce at least 60 percent of acid value ofsaid oxidation product; said oxidation product of hydrocarbon beingprepared by contacting at 100 to 180 C. aliphatic hydrocarbon of 15 to55 carbon atoms with molecular oxygen; and said epoxy compound havingthe formula of R 3 1 R \I{ wherein R is one member of the groupconsisting of hydrogen atom, alkyl group of 1 to 10 carbon atoms,hydroxymethyl group, chloromethyl group, acyloxymethyl group of 2 to 7carbon atoms, carboalkoxymethyl group of 2 to 7 carbon atoms,alkoxymethyl group of 2 to 7 carbon atoms, phenoxymethyl group andphenyl group and R and R are respectively one member of the groupconsisting of hydrogen atom and a lower alkyl group of 1 to 3 carbonatoms, and when R and R are alkyl group and R is hydrogen and R and Rmay constitute a cycloalkyl group being bonded to each other at theirend positions.

2. The process for cold rolling according to claim 1, in which saidaddition compound has an acid value of 2 to 20.

3. The process for cold rolling according to claim 1, in which saidoxidation product of aliphatic hydrocarbon has an acid value of 50 to100.

4. The process for cold rolling according to claim 1 in which said epoxycompound is one member of the group consisting of epoxyethane,epoxypropane, 1,2-epoxy- :butane, 2,3-epoxybutane, epoxyisobutane,1-oxy-2,3- epoxypropane, epichlorohydrine, 1,2-epoxycyclohexane, styreneoxide and phenyl glycidyl ether.

5. The process for cold rolling according to claim 1 in which said epoxycompound has the formula of wherein R is one member of the groupconsisting of hy drogen atom, methyl group and ethyl group.

6. A process for cold rolling a metal which comprises applying betweenthe roll and the metal an aqueous dispersion having dispersed therein 1to 30% by weight of Water of a lubricating amount of the additionproduct of an epoxy compound and an oxidation product of an aliphatichydrocarbon having an acid value of 30 to 11.0; said addition producthaving an average molecular yweight'of 280 to 800 and an acid value oft)to 30 and containing said epoxy compound in the molecule in anamount-from 1 to 2 moles per mole of carboxyl group in the oxidationproduct but sufficient to reduce at least percent of acid value of saidoxidation product; said oxidation product of hydrocarbon being preparedby contacting at to C. aliphatic hydrocarbon of 15 to 55 carbon atomswith molecular oxygen; and said epoxy compound having the formula of pwherein R is one member of the group consisting of hydrogen atom, alkylgroup of 1 ,to 10 carbonatoms, hydroxymethyl group, chloromethyl group,acyloxymethyl group of 2 to 7 carbon atoms, carboalkoxymethyl group of 2to 7 carbon atoms, alkoxymethyl' group of 2 to 7 carbon atoms,phenoxymethyl group and phenyl group and R and R are respectively onemember of the group consisting of hydrogen atom and a lower alkyl groupof 1 to 3 carbon atoms, and when R andR' are alkyl group and R ishydrogen and R and R may constitute a cycloalkyl group by being bondedto each other at their end positions. f

References Cited UNITED STATES PATENTS 10/ 1954 Great Britain 252-493DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner V US.Cl. x11. 252-55, 52, 56 R

